Water dispersable chlorinated solvent and method

ABSTRACT

The invention disclosed provides a new improved water dispersable chlorinated solvent and method for cleaning surfaces by high pressure.

United States Patent [1 1 Ritzi Dec. 9, 1975 [54] WATER DISPERSABLE CHLORINATED 3.501.373 3/1970 illingworth 252/171 ux SOLVENT ANDMETHOD 1535,!60 lO/l970 Arger 134/22 3,553,145 l/197I Bulke el al. 252/364 [75] Inventor: Jack Henry Ritzi, Hamilton, Ohio 3.831010 9/1974 McDermolt el al, r. 134/22 [73] Assignee: W. R. Grace & Co., New York,

Primary Examiner-William E. Schulz [22] Filed: Feb. 19, 1975 Attorney, Agent, or Firm-Eugene Mr Bond [21] Appl. No.: 551,218

[52] U.S. Cl. 252/17]; 134/22; 252/309 {57] ABSTRACT [51] Int. Cl. CllD 7/50 Field Search The invention disclosed provides a new improved 25 /3 134/22, 24. 34 water dispersable chlorinated solvent and method for cleaning surfaces by high pressure. [56] References Cited UNITED STATES PATENTS 5 Chin's, No Drawings 3,434,881 3/!969 Smith l34/22 WATER DISPERSABLE CHLORINATED SOLVENT AND METHOD The present invention relates to a new method and composition for cleaning the interior of a container vessel by means of high pressure sprays.

In summary, this invention provides for cleaning surfaces with cleaning compositions comprising applying an aqueous solution containing the cleaning composi- ,tion to the surface to be cleaned, and rinsing the composition from the surface with water.

Spray cleaning of surfaces such as interiors of tank trucks, railway tank cars, storage tanks, mixing kettles, ships holds, and other similar areas has been used where the drying or curing of paints or resinous soils make it impossible to clean by the usual chemical cleaning operations. In general, strong, hot caustic solutions have been used to remove these soils and are generally ineffective.

The present composition has been found to be highly effective by providing a water dispersable solvent which can be used through standard high pressure, high temperature equipment for removing resins or other soils which conventional cleaning solutions will not remove. This composition can also be applied as an additive to standard caustic solutions.

Cleaning is done using a blend of chlorinated solvents dispersed in hot water rather than spraying them undiluted and cold. The present composition accomplishes suspension of the blend of solvents rather than emulsification.

The present composition, generally stated, comprises a blend containing from O to about 75% methylene chloride, from about 25 to about 99.9% of low volatility chlorinated solvent such as orthodichlorobenzene, propylenedichloride or trichloro-ethylene, and from about 0.1 to about 25% of emulsifier which is added from about 1 to about 25% concentration to hot water or to a standard caustic solution at 120 to 190 F. A standard cleaning operation at this temperature will remove almost any soil from a containers interior. The emulsifier or combination of emulsifiers in the formulation should be in sufficient concentration only to briefly suspend droplets of solvent in the water. The turbulence caused by the cleaning operation will keep the solvent suspended and the solvency of the solvents will not be lost by tying them too tightly into the water solution.

When used herein, all parts are given by weight unless indicated otherwise.

The present composition also contains an emulsifier such as an alkyl benzene sulfonate having from 8 l8 carbons in the alkyl group. Suitable alkylbenzene sulfonates include the tetrapropylene benzene sulfonate and linear alkylbenzene sulfonates having about 12 carbons in the alkyl group, the latter being preferred because they are biodegradable and do not create disposal problems.

The composition may also contain an emulsifier such as phosphate esters, alkali metal and preferably sodium salts, sold under the trade name Emcol PS-222 by Witco Chemical Co. of New York City, and alkoxylated alkyl phosphate esters having from 6-18 carbons,

2 preferably from 10 to 14 carbons, in the alkyl group and from 2-6, and preferably 4 moles of alkoxylate. The preferred alkoxylate is ethylene oxide.

In addition, a combination of emulsifiers can be used such as an alkyl sulfonate having from 16 to 20 carbons in the alkyl group combined with an alkyl benzene sulfonate having from 12 to 16 carbons in the alkyl group. Suitable alkyl sulfonates include sulfonated castor oil having about 18 carbons in the alkyl group. Suitable alkyl benzene sulfonates include the benzene sulfonate of myristic acid having about 14 carbons in the alkyl group.

The cleaning composition may contain the alkali metal (sodium, potassium and amine) salts of fatty acid sulfonates having from 8-18 carbons in the fatty acid group, and lower alkyl benzene sulfonate having from 1-3 carbons in a lower alkyl group. The preferred fatty acid sulfonate is the amine salt of lauroleic acid sulfonate or dodecanoil acid sulfonate. The preferred lower alkylbenzene sulfonates include xylene, toluene, ethylbenzene, and isopropylbenzene sulfonates. Sulfonates made from xylene include orthoxylene sulfonate, metaxylene sulfonate, paraxylene sulfonate, and ethylbenzene sulfonate. Commercial xylene sulfonates usually contain metaxylene sulfonate as the main ingredient.

Additional useful emulsifiers include materials such as phosphate esters, sodium salt of a coconut derived dicarboxylate, sulfonated castor oil, sulfated caster oil, ethoxylated monolaurate, lauric alkylolamines and the like mixtures of these various materials may also be used.

The critical factor of the emulsifier used herein is that it be sufficiently low in concentration and yet effective to suspend the major portion of the solvents for a period of time from about 0.5 to about 5 minutes.

The preferred compositions according to this invention are shown in Table A.

TABLE A INGREDIENT PARTS BY WElG HT Methylene Chloride O40.0% Low Volatile Chlorinated Solvent (propylenedichloride) GOO-99.5% Emulsifier (alkyl benzene sulfonate) 0.5-10.0%

EXAMPLE 1 1 X 2 inch steel panels were coated with two moderately difiicult to remove resins and one very dimcult to remove resin and allowed to air cure for a 16 hour period at room temperature. The panels were then immersed in the dispersions below for V2 hour at the temperatures noted and then rinsed. The dispersions were periodically stirred:

TABLE B PARTS PARTS INGREDIENT BY WEIGHT BY WEIGHT Water 95.00 92.5 Caustic Cleaner 7.5 Alkyl sulfonute 0.l Sulfonated Castor Oil 0.15 Methylene Chloride L Propylene Dichloride 3.15

100.00 l00.00 Temperatures I20F to IF to 140F. [F RESULTS Resin No. I (Rohm & Haas Acryloid A-IOI) Removed Slightly Softened Resin No. 2 (Rohm 8c Haas PIA-8 Latex) Removed Removed Resin No. 3 (Rohm 8i Haas P-68l Resin) Removed Removed Similar results were obtained when the alkyl sulfonate and sulfonated castor oil were re laced with the P EXAMPLE 3 following:

I. 0.3% dimethyl dicoco ammonium chloride 2. 1.0% sulfonated caster oil 3. 0.3% phosphate ester TABLE D INGREDIENTS PARTS BY WEIGHT PARTS BY WEIGHT Methylene Chloride Propylene Dichloride An Alkyl benzene sulfonate Dilution medium Resin No. I (Rohm & Haas I000 7.5% caustic cleaner Water solution RESULTS Almost l00% removed Almost IOO% Removed Acryloid A- l OI Resin No. 4 (Glidden Removed Removed Oleoresinous Can Coating) Resin No. 5 (Glidden Greatly Softened Greatly Softened Vinyl Can Coating) 4. 0.2% dodecyl benzene sulfonate 5. 0.6% phosphate ester 0.4% nonyl phenol EXAMPLE 2 The following were dispersed in water at the given concentrations and the same cleaning test as in Example 1 above was run at 120 to l40F.. The two moderately difficult to remove resins were replaced with two difficult to remove resins.

TABLE C PARTS PARTS PARTS PARTS INGREDIENTS BY WEIGHT BY WEIGHT BY WEIGHT BY WEIGHT Methylene chloride 33.0 32.0 23.0 I Propylene dichloride 67.0 65.0 47.0 38.0 Phosphate ester 3.0 18.0 25.0 Ethoxylated nonyl phenol 12.0 |8.0

IO0.0 i000 100.0 100.0 I: Emulsified in 7.5% cleaner solution 5.0% 5.0% 6.9% 8.5% RESULTS Amount of settling during cleaning operation Extensive Extensive Some None Resin No. I (Rohm 8L Haas Greatly Almost No Acryloid A401 Softened Some Soften- Efi'ect Removed ing Resin No. 4 (Gliden Removed Removed Removed Greatly Oleoresinous Can Coating) Softened Resin No. 5 (Glidden Softened Removed Softened Slightly Softened Vinyl Can Coating) about 0.] to about 25% by weight of an emulsifier, said blend being disposed in water in an amount from about 1 to about 25% by weight and applied to the surface at a temperature of 120F. to 190F., and thereafter rinsing the applied solution from the surface with water.

2. The method of claim 1 wherein the chlorinated solvent is a member of the group consisting of orthodichlorobenzene, propylenedichloride and trichloroethylene.

3. The method of claim 1 wherein the emulsifier maintains an emulsion for a period of time from about 0.5 to about 5 minutes.

4. A cleaning composition which comprises in com bination from 0% to about by weight methylene chloride, from about 25% to about 99.9% by weight of a low volatility chlorinated solvent selected from the group consisting of orthodichlorobenzene propylenedichloride and trichloro-ethylene, and from about 0.1 to about 25% by weight of an emulsifier capable of maintaining an emulsion for a period of time for about 0.5 to about 5 minutes in water at a cleaning composition concentration of l to about 25% by weight.

5. The composition of claim 4 wherein the emulsifier is alkyl benzene sulfonate having from 8-18 carbon atoms in the alkyl group.

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,925, 231 DATED Dec. 9, 1975 |NV ENTOR(S) 1 Jack Henry Ritzi It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Correct listed assignee "W. R. Grace & Co. New York, N. Y.

to reflect true assignee of record Chemed Corporation,

DuBOis Tower, Cincinnati, Ohio Signed and Scaled this sixteenth Day of March 1976 [SEAL] Arrest:

RUTH C. MASON C. MARSHALL DANN AMP-Hing 01TH? (ummr'ssimwr uflarems and Trademarks 

1. A METHOD FOR CLEANING SURFACES WHICH COMPRISES APPLYING A BLEND OF FROM 0% TO ABOUT 75% BY WEIGHT METHYLENE CHLORIDE, FROM ABOUT 25 TO ABOUT 99.9% BY WEIGHT OF A LOW VOLATIBITY CHLORINATED SOLVENT, AND FROM ABOUT 0.1 TO ABOUT 25% BY WEIGHT OF AN EMULSIFIER, SAID BLEND BEING DISPOSED IN WATER IN AN AMOUNT FROM ABOUT 1 TO ABOUT 25% BY WEIGHT AND APPLIED TO THE SURFACE AT A TEMPERATURE OF 120*F. TO 190*F., AND THEREAFTER RINSING THE APPLIED SOLUTION FROM THE SURFACE WITH WATER.
 2. The method of Claim 1 wherein the chlorinated solvent is a member of the group consisting of orthodichlorobenzene, propylenedichloride and trichloro-ethylene.
 3. The method of claim 1 wherein the emulsifier maintains an emulsion for a period of time from about 0.5 to about 5 minutes.
 4. A cleaning composition which comprises in combination from 0% to about 75% by weight methylene chloride, from about 25% to about 99.9% by weight of a low volatility chlorinated solvent selected from the group consisting of orthodichlorobenzene propylenedichloride and trichloro-ethylene, and from about 0.1 to about 25% by weight of an emulsifier capable of maintaining an emulsion for a period of time for about 0.5 to about 5 minutes in water at a cleaning composition concentration of 1 to about 25% by weight.
 5. The composition of claim 4 wherein the emulsifier is alkyl benzene sulfonate having from 8-18 carbon atoms in the alkyl group. 